CN101880066A - Preparation method of high-density high-safety long-life lithium cobaltate - Google Patents
Preparation method of high-density high-safety long-life lithium cobaltate Download PDFInfo
- Publication number
- CN101880066A CN101880066A CN 201010204429 CN201010204429A CN101880066A CN 101880066 A CN101880066 A CN 101880066A CN 201010204429 CN201010204429 CN 201010204429 CN 201010204429 A CN201010204429 A CN 201010204429A CN 101880066 A CN101880066 A CN 101880066A
- Authority
- CN
- China
- Prior art keywords
- preparation
- lithium cobaltate
- density
- safety long
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a preparation method of high-density high-safety long-life lithium cobaltate, which comprises the following steps of: adding a fluxing agent in the first high-temperature reaction process of the two-stage preparation method of lithium cobaltate so that the interfacial tension between two raw materials is reduced to achieve better fusion, produce crystal nucleus more easily, shorten crystal growth time, further shorten high-temperature reaction time and increase density; and coating one nanometer semiconductor material layer by adopting a dry method in the second high-temperature process so as to increase the electrochemical properties, the safety and the cycle life of lithium cobaltate. The prepared lithium cobaltate product has large granules, high compacted density, excellent electrochemical properties, convenient reaction process operations, low energy consumption and low cost.
Description
Technical field
The present invention relates to lithium ion battery, particularly a kind of preparation method of high-density high-safety long-life lithium cobaltate.
Background technology
Lithium-ion secondary cell has the operating voltage height, energy density is big, self-discharge rate is little, the electrochemistry cycle characteristics can wait advantage well, not only be used widely, and all demonstrate good prospects for application in power truck, weaponry, space flight and other field at aspects such as mobile telephone, notebook computer, portable electronics.From the lithium-ion secondary cell commercialization, its positive electrode material has just adopted cobalt acid lithium.Though because the cobalt resource scarcity causes cobalt acid lithium price height, and with cobalt acid lithium is the security hidden danger that the anodal battery has the use aspect, but cobalt acid lithium is reliable because of its volume energy density height, stable electrochemical property and technology, is still the positive electrode active materials of the main employing of commodity lithium ion battery at present.And in order further to improve with cobalt acid lithium is the performance of the lithium ion battery of positive active material, people have carried out more deep research to cobalt acid lithium, expectation can further improve the chemical property and the safety performance of cobalt acid lithium, and promoting with cobalt acid lithium is the over-all properties of anodal lithium ion battery.The restriction that has been subjected to the material own characteristic because of cobalt acid lithium specific storage can't continue to promote, and existing market is at the high-end lithium ion battery of constantly pursuing high energy density per unit volume.Battery producer also requires positive electrode material can have higher density when optimizing battery structure and realizes high energy density per unit volume.Simultaneously, for the further application of developing lithium cobaltate cathode material lithium ion battery in high-end fields such as power, satellite and military equipment, also must improve the safety performance and the cycle life of cobalt acid lithium.
At present domestic highdensity cobalt acid lithium material is synthetic mainly to be repeatedly to calcine and pulverize, and expend lot of energy, and process time is long, and cost is than higher, and institute's synthetic cobalt acid lithium product particle diameter is little, has potential safety hazard.
Summary of the invention
For satisfying above-mentioned development need, the invention provides a kind of preparation method of high-density high-safety long-life lithium cobaltate.
The preparation method of high-density high-safety long-life lithium cobaltate of the present invention, its processing step is as follows:
1) with Li
2CO
3, Co
3O
4Mix with certain proportion with fusing assistant;
2) with said mixture Synthetic 2-15h under 900-1100 ℃ of condition;
3) method that adopts the high speed swirling flow to pulverize the synthetic material is pulverized, and obtains the moderate product of particle diameter;
4) with the 3rd) step in product and nano semiconductor material mix Synthetic 2-20h under 500-1100 ℃ of preparation process by a certain percentage.
5) the synthetic product is carried out crushing and classification.
Described fusing assistant is one or both mixtures in magnesium oxide, magnesium fluoride, calcium oxide, Calcium Fluoride (Fluorspan), Sodium Tetraborate and the lithium tetraborate, the part by weight that fusing assistant accounts for whole material for greater than 0% less than 10%.
Described nano semiconductor material is one or both in zinc oxide, zinc sulphide, zinc selenide, silicon-dioxide, Niobium Pentxoxide, tin indium oxide and the tindioxide, the granular size of nano semiconductor material is 10-1000nm, nano semiconductor material account for whole material's proportion for greater than 0% less than 10%.
Adopt the cobalt acid lithium product particle of method preparation of the present invention big, the tamped density in pole piece is greatly improved, and has improved the safety performance and the cycle life of material simultaneously.The density that in the past improved product be by repeatedly repeatedly the method for high temperature sintering realize, the repeated multiple times sintering can make the product processes complexity, and it is huge to consume energy, and cost increases, the present invention overcomes these shortcomings, obtains high density product by very simple and practical method.Coat one deck nano semiconductor material at skin, increase the particle diameter of product simultaneously, improved cobalt acid lithium security of products energy and cycle life.
The present invention adopts the method that adds special fusing assistant and clad nano semiconductor material to prepare cobalt acid lithium, fusing assistant can reduce the interfacial tension between liquid tricobalt tetroxide and the Quilonum Retard, make its better fusion, at the easier generation nucleus of lesser temps, shorten the crystal growth time, and then shorten the pyroreaction time, reduce cost.Surface coated nano semiconductor material can allow the lithium ion free migration, can not have influence on its chemical property in the safety performance that improves cobalt acid lithium.Adopt the cobalt acid lithium product of these two kinds of method preparations in a kind of technology simultaneously, particle diameter is big, pole piece compacted density height, and cycle performance and safety performance are good.Adopt middle particle diameter 12～15 μ m of the cobalt acid lithium of method preparation of the present invention, compacted density＞4.2g/cm
3, 1C specific discharge capacity＞155mAh/g, 100 circulation volume conservation rate＞95%.Adopt the cobalt acid lithium of the present invention's preparation not only can be applied on the products such as mobile telephone, notebook computer, portable electronics, can also further be generalized to military domain, comprise weaponry, satellite and other spacecraft.
Description of drawings
Fig. 1 is the preparation method's of a high-density high-safety long-life lithium cobaltate of the present invention process route chart.
Embodiment
Below in conjunction with the preparation method do more detailed explanation of embodiment to high-density high-safety long-life lithium cobaltate of the present invention.
Fig. 1 is the preparation method's of high-density high-safety long-life lithium cobaltate a process route chart.
Embodiment 1
With Li
2CO
3And Co
3O
4Ratio and MgO in Li/Co=1.03 mix, and it is 0.3% that MgO accounts for whole material's proportion.Mixture is at 1000 ℃ of following sintering 8h, and the method that the cooling back adopts the high speed swirling flow to pulverize is pulverized, with the material after pulverizing with after 1% nano zine oxide mixes at 900 ℃ of following sintering 5h, after the cooling material is carried out crushing and classification, obtain product.The middle particle diameter of its product is 12.3 μ m, and the 1C specific discharge capacity is 155.7mAh/g, and compacted density is 4.3g/cm
3, 100 times the circulation volume conservation rate is 95.3%.
Embodiment 2
With Li
2CO
3And Co
3O
4Mix in the ratio of Li/Co=1.04 and Sodium Tetraborate and lithium tetraborate, it is 1.0% that Sodium Tetraborate and lithium tetraborate account for whole material's proportion.Mixture is at 950 ℃ of following sintering 8h, and the method that the cooling back adopts the high speed swirling flow to pulverize is pulverized, with the material after pulverizing with after 0.5% nano-stannic oxide mixes at 900 ℃ of following sintering 8h, after the cooling material is carried out crushing and classification, obtain product.Particle diameter is 13.7 μ m in its product, and the 1C specific discharge capacity is 157.2mAh/g, and compacted density is 4.25g/cm
3, 100 times the circulation volume conservation rate is 96.3%.
Embodiment 3
With Li
2CO
3And Co
3O
4Ratio and Calcium Fluoride (Fluorspan) in Li/Co=1.05 mix, and it is 0.2% that Calcium Fluoride (Fluorspan) accounts for whole material's proportion.Mixture is at 1030 ℃ of following sintering 10h, and the method that the cooling back adopts the high speed swirling flow to pulverize is pulverized, with the material after pulverizing with after 0.3% nano-indium stannum oxide mixes at 980 ℃ of following sintering 8h, after the cooling material is carried out crushing and classification, obtain product.Particle diameter is 14.6 μ m in its product, and the 1C specific discharge capacity is 155.6mAh/g, and compacted density is 4.25g/cm
3, 100 times the circulation volume conservation rate is 96.0%.
Embodiment 4
With Li
2CO
3And Co
3O
4Ratio and magnesium fluoride in Li/Co=1.02 mix, and it is 0.5% that magnesium fluoride accounts for whole material's proportion.Mixture is at 1000 ℃ of following sintering 10h, the method that the cooling back adopts the high speed swirling flow to pulverize is pulverized, material after pulverizing is mixed with 0.5% nanometer zinc selenide and 0.5% Niobium Pentxoxide afterwards at 850 ℃ of following sintering 8h, after the cooling material is carried out crushing and classification, obtain product.Particle diameter is 12.1 μ m in its product, and the 1C specific discharge capacity is 156.2mAh/g, and compacted density is 4.28g/cm
3, 100 times the circulation volume conservation rate is 95.8%.
Embodiment 5
With Li
2CO
3And Co
3O
4Mix in the ratio of Li/Co=1.03 and Sodium Tetraborate and lithium tetraborate, it is 0.8% that Sodium Tetraborate and lithium tetraborate account for whole material's proportion, mixture is at 950 ℃ of following sintering 10h, the method that the cooling back adopts the high speed swirling flow to pulverize is pulverized, material after pulverizing is mixed afterwards at 1030 ℃ of following sintering 6h with 0.8% nano-stannic oxide and 0.2% tin indium oxide, after the cooling material is carried out crushing and classification, obtain product.Particle diameter is 13.1 μ m in its product, and the 1C specific discharge capacity is 158.7mAh/g, and compacted density is 4.22g/cm
3, 100 times the circulation volume conservation rate is 97.1%.
Claims (5)
1. the preparation method of a high-density high-safety long-life lithium cobaltate, it is characterized in that: described preparation method's processing step is as follows:
1) with Li
2CO
3, Co
3O
4Mix with certain proportion with fusing assistant;
2) with said mixture Synthetic 2-15h under 900-1100 ℃ of condition;
3) method that adopts the high speed swirling flow to pulverize the synthetic material is pulverized, and obtains the moderate product of particle diameter;
4) with the 3rd) step in product and nano semiconductor material mix Synthetic 2-20h under 500-1100 ℃ of condition by a certain percentage.
5) the synthetic product is carried out crushing and classification.
2. the preparation method of high-density high-safety long-life lithium cobaltate according to claim 1, it is characterized in that: described fusing assistant is one or both mixtures in sodium oxide, potassium oxide, magnesium fluoride, calcium oxide, Calcium Fluoride (Fluorspan), Sodium Tetraborate and the lithium tetraborate.
3. the preparation method of high-density high-safety long-life lithium cobaltate according to claim 1, it is characterized in that: described nano semiconductor material is one or both in zinc oxide, zinc sulphide, zinc selenide, silicon-dioxide, tin indium oxide and the tindioxide.
4. the preparation method of high-density high-safety long-life lithium cobaltate according to claim 3 is characterized in that: the part by weight that described fusing assistant accounts for whole material for greater than 0% less than 10%.
5. the preparation method of high-density high-safety long-life lithium cobaltate according to claim 4, it is characterized in that: the granular size of described nano semiconductor material is 10-1000nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102044294A CN101880066B (en) | 2010-06-21 | 2010-06-21 | Preparation method of high-density high-safety long-life lithium cobaltate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102044294A CN101880066B (en) | 2010-06-21 | 2010-06-21 | Preparation method of high-density high-safety long-life lithium cobaltate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101880066A true CN101880066A (en) | 2010-11-10 |
| CN101880066B CN101880066B (en) | 2012-01-25 |
Family
ID=43052236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102044294A Active CN101880066B (en) | 2010-06-21 | 2010-06-21 | Preparation method of high-density high-safety long-life lithium cobaltate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101880066B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000881A (en) * | 2012-12-18 | 2013-03-27 | 江苏菲思特新能源有限公司 | Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material |
| CN104810512A (en) * | 2015-05-06 | 2015-07-29 | 中信国安盟固利电源技术有限公司 | Coated and modified anode material and preparation method thereof |
| CN106169578A (en) * | 2016-08-23 | 2016-11-30 | 金川集团股份有限公司 | A kind of preparation method of big granularity lithium cobaltate cathode material |
| CN106848293A (en) * | 2017-01-10 | 2017-06-13 | 上海电力学院 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
| CN109085033A (en) * | 2018-08-17 | 2018-12-25 | 珠海格力电器股份有限公司 | A kind of complicated difficult soluble noble metal standard sample preparation method and its content test method |
| CN109786681A (en) * | 2017-12-28 | 2019-05-21 | 湖南长远锂科有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof of conductive compound coating layer |
| CN113851622A (en) * | 2021-09-14 | 2021-12-28 | 厦门大学 | Protective layer of battery system and electrochemical device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05266889A (en) * | 1992-03-23 | 1993-10-15 | Matsushita Electric Ind Co Ltd | Manufacture of positive electrode active material and nonaqueous electrolyte secondary battery using same material |
| CN1719643A (en) * | 2005-07-08 | 2006-01-11 | 清华大学 | Macro-grain LiCoO2 of anode material for lithium ion cell and preparing process thereof |
-
2010
- 2010-06-21 CN CN2010102044294A patent/CN101880066B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05266889A (en) * | 1992-03-23 | 1993-10-15 | Matsushita Electric Ind Co Ltd | Manufacture of positive electrode active material and nonaqueous electrolyte secondary battery using same material |
| CN1719643A (en) * | 2005-07-08 | 2006-01-11 | 清华大学 | Macro-grain LiCoO2 of anode material for lithium ion cell and preparing process thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Solid State Ionics》 20021231 Zhaoxiang Wang et al. Structural and electrochemical characterizations of surface-modified LiCoO2 cathode materials for Li-ion batteries 335-342 1-5 第148卷, 2 * |
| 《中南大学学报(自然科学版)》 20040229 彭文杰 等 固相合成条件对LiCoO2 结构与形貌的影响 59-64 1-5 第35卷, 第1期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000881A (en) * | 2012-12-18 | 2013-03-27 | 江苏菲思特新能源有限公司 | Positive material, namely tin-doped lithium cobalt oxide, for lithium ion cell, and preparation method of positive material |
| CN104810512A (en) * | 2015-05-06 | 2015-07-29 | 中信国安盟固利电源技术有限公司 | Coated and modified anode material and preparation method thereof |
| CN106169578A (en) * | 2016-08-23 | 2016-11-30 | 金川集团股份有限公司 | A kind of preparation method of big granularity lithium cobaltate cathode material |
| CN106848293A (en) * | 2017-01-10 | 2017-06-13 | 上海电力学院 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
| CN109786681A (en) * | 2017-12-28 | 2019-05-21 | 湖南长远锂科有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof of conductive compound coating layer |
| CN109786681B (en) * | 2017-12-28 | 2021-03-16 | 湖南长远锂科股份有限公司 | Lithium ion battery anode material with conductive composite coating layer and preparation method thereof |
| CN109085033A (en) * | 2018-08-17 | 2018-12-25 | 珠海格力电器股份有限公司 | A kind of complicated difficult soluble noble metal standard sample preparation method and its content test method |
| CN113851622A (en) * | 2021-09-14 | 2021-12-28 | 厦门大学 | Protective layer of battery system and electrochemical device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101880066B (en) | 2012-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101880066B (en) | Preparation method of high-density high-safety long-life lithium cobaltate | |
| CN104272523B (en) | A kind of zinc ion rechargeable battery and its manufacture method | |
| CN105958032B (en) | A kind of method and application improving zinc ferrite chemical property by doping nickel element | |
| CN102569781B (en) | High-voltage lithium ion battery cathode material and preparation method thereof | |
| CN104993125B (en) | A kind of lithium ion battery negative material Fe3O4The preparation method of/Ni/C | |
| CN101950804B (en) | Method for preparing spherical SnS2 anode material of lithium ion battery | |
| CN104377353B (en) | A kind of preparation method of LiFePO4 and nickel cobalt lithium manganate | |
| CN101546826B (en) | Preparation method for spherical lithium ferric phosphate used as lithium ion battery anode material | |
| CN102760885A (en) | Tin-base complex oxide/graphene composite material, and preparation method and application thereof | |
| CN102522542A (en) | Elemental sulfur composite material containing graphene and preparation method thereof | |
| CN103078087A (en) | Preparation method of lithium titanate/carbon nano tube composite cathode material | |
| CN101771145A (en) | Method for preparing multielement cathode materials for lithium ion batteries | |
| CN108878826A (en) | A kind of sodium manganate/graphene combination electrode material and its preparation method and application | |
| CN106935830A (en) | A kind of lithium ion battery composite cathode material and its preparation method and application | |
| CN105702956A (en) | Negative material for sodium-ion battery and preparation method of negative material | |
| CN102079530A (en) | Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology | |
| CN103466722B (en) | Synthesis technology of nano cobalt oxyhydroxide | |
| CN101834287B (en) | Preparation method of anode material of lithium ion battery | |
| CN104124447B (en) | A kind of New Co (OH) F lithium ion battery cathode material and its preparation method | |
| CN102079517A (en) | Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method | |
| CN101699640A (en) | Fe/FeO composite negative electrode material of power lithium ion battery and preparation method thereof | |
| CN115911577B (en) | Preparation method of solid sodium ion battery | |
| CN103435108B (en) | Process for synthesizing large-granular spherical lithium cobalt oxide with high tap density | |
| CN103956463B (en) | The preparation method of a kind of LiFePO4-manganese oxide lithium binary anode material of lithium battery | |
| CN109768234A (en) | A kind of cobalt doped strontium titanates/graphene composite material, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 102200 Beijing city Changping District Bai Fu Road 18 Patentee after: Beijing mengguli New Material Technology Co.,Ltd. Address before: 102200 Beijing city Changping District Bai Fu Road 18 Patentee before: CITIC GUOAN MENGGULI POWER SOURCE TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |